University of Southampton Research Repository Eprints Soton

Total Page:16

File Type:pdf, Size:1020Kb

University of Southampton Research Repository Eprints Soton University of Southampton Research Repository ePrints Soton Copyright © and Moral Rights for this thesis are retained by the author and/or other copyright owners. A copy can be downloaded for personal non-commercial research or study, without prior permission or charge. This thesis cannot be reproduced or quoted extensively from without first obtaining permission in writing from the copyright holder/s. The content must not be changed in any way or sold commercially in any format or medium without the formal permission of the copyright holders. When referring to this work, full bibliographic details including the author, title, awarding institution and date of the thesis must be given e.g. AUTHOR (year of submission) "Full thesis title", University of Southampton, name of the University School or Department, PhD Thesis, pagination http://eprints.soton.ac.uk UNIVERSITY OF SOUTHAMPTON FACULTY OF SCIENCE DEPARTMENT OF CHEMISTRY Doctor of Philosophy CHEMICAL AND ELECTROCHEMICAL NITRATIONS OF ALKENES AND DIENES by Andrew Jonathan Bloom ACKNOWLEDGEMENT I wish to thank the following: My parents for their support; Dr. John Mellor and Professor Martin Fleischmann, my supervisors; Dr. Philip Parsons for his faith and encouragement; Neil Smith, Ivan Pinto, Jeff Buchannan and Neil Carlson for the proof-reading and Suzanne Salt for the typing. Financial support from The Procurement Executive, Ministry of Defence, for my maintenance grant, and NATO, for travel expenses, is gratefully acknowledged. Table of Contents Chapter 1 Introduction 1 I'l Electrochemical Nitration 5 1-1,1 Anodic Oxidation of Dinitrogen Tetroxide 6 1*1,2 Anodic Oxidation of the Nitrite Ion 8 1-1,3 Anodic Oxidation of the Nitrate Ion 10 1-2 The Nitration of Alkenes and Dienes 12 1-2,1 The Reaction of Alkenes with Nitronium Salts 14 1-2,2 The Reaction of Acetyl Nitrate with Alkenes and Dienes 32 1-2,3 The Reaction of Dinitrogen Pentoxide with Alkenes and Dienes 46 1-2,4 The Reaction of Nitric Acid with Alkenes and Dienes 48 1-2,5 The Reaction of Tetranitromethane with Alkenes and Dienes 55 1-2,6 The Reaction of Nitryl Fluoride with Alkenes 60 1-2,7 The Reaction of Nitryl Chloride and Dinitrogen Tetroxide-Chlorine with Alkenes and Dienes 61 1-2,8 The Reaction of Nitryl Iodide and Dinitrogen Tetroxide with Alkenes and Dienes 63 1-2,9 The Reaction of Dinitrogen Tetroxide with Alkenes and Polyenes 65 1-2,10 The Reaction of Mercuric Nitrite with Alkenes 70 1-3 Initial Objectives 71 Chapter 2 The Electrogeneration of Nitronium Salts and Dinitrogen Pentoxide and Their Reactions 73 2-1 Introduction and Background 74 2"1,1 Mediated or Redox Catalysed Reactions 74 2-1,2 Electrochemically Generated Reagents 78 2-1,3 Chemical Preparation of Nitronium Salts and Dinitrogen Pentoxide 82 2-2 Results and Discussion i 84 2-2,1 Choice of Solvents 84 2-2,2 Choice of Electrolyte 85 2-2,3 Cell Design 86 2-2,4 Assay 88 2-2,5 Preparation and Reactions of Nitronium Tetrafluoroborate in Acetonitrile 89 2-2,6 Preparation and Reactions of Nitronium Hexafluorophosphate in Nitromethane 96 2-2,7 Generation of Nitronium Tetrafluoroborate in Sulpholane 101 2-2,8 Generation of Dinitrogen Pentoxide in Acetonitrile and Dichloromethane 101 2-3 Conclusions 109 Chapter 3 Nitroacetamidation of Alkenes and Dienes 110 3-1 Introduction and Background 111 3-1,1 Acetamidation Reactions: The Reaction of Electrophiles with Alkenes in Acetonitrile 111 3-1,2 Preparation of Vicinal Nitroamines 120 3-2 Results and Discussion 3-2,1 The Nitroacetamidation of Alkenes 124 3*2,2 The Nitroacetamidation of Dienes 140 3-2,3 Some Transformations of Nitroacetamides 152 3*3 Conclusions 157 Chapter 4 The Preparation of 1-Nitro-l,3-dienes Via the Nitrotrifluoroacetoxylation of Dienes 158 4*1 Introduction and Background 159 4*1,1 Reactions of Trifluoroacetyl Nitrate 159 4*1,2 Additions Involving the Trifluoroacetate Ion 160 4*1,3 Literature Preparations of 1-Nitro-l,3-Dienes 162 4*2 Results and Discussion 167 4*2,1 The Nitrotrifluoroacetoxylation of Dienes and the Preparation of 1-Nitro-l,3-dienes 167 4*2,2 The Nitrotrifluoroacetoxylation of Alkenes 174 4*2,3 Nucleophilic Additions to 1-Nitro-l,3-dienes 178 4*3 Conclusions 181 Chapter 5 Experimental Procedures 182 5*1 Materials 183 5*1,1 Purification of Solvents 183 5*1,2 Preparation and/or Purification of Electrolytes 183 5*1,3 Preparation and/or Purification of Starting Materials 183 5*1,4 Handling of Dinitrogen Tetroxide 184 5*1,5 Purification and Handling of Nitronium Tetrafluoroborate 184 5*1,6 Preparation and/or Purification of Other Reagents 185 5*1,7 Apparatus and Equipment 185 5*2 Electrochemistry Experiments 187 5*2,1 Typical Electrolysis Method 187 5-2,2 Analytical Method 187 5*2,3 Reactions of Electrogenerated Nitronium Tetrafluoroborate 189 5-2,4 Reactions of Electrogenerated Nitronium Hexafluorophosphate 191 5*2,5 Reaction of Electrogenerated Dinitrogen Pentoxide 193 5*3 The Nitroacetamidation of Alkenes 193 5*3,1 The Epimerisation of Nitroacetamides 202 5*3,2 The Reduction of Nitroacetamides 204 5*4 The Nitroacetamidation of Dienes 207 5*5 Oxidation and Reduction Reactions 215 5*6 Nitrotrifluoroacetoxylation: The Preparation of Nitrodienes 220 5*6,1 Typical Nitrotrifluoroacetoxylation Procedure 220 5*6,2 Typical Elimination Procedure 222 5*6,3 Nucleophilic Addition Reactions 227 References 230 UNIVERSITY OF SOUTHAMPTON ABSTRACT FACULTY OF SCIENCE CHEMISTRY Doctor of Philosophy CHEMICAL AND ELECTROCHEMICAL NITRATION OF ALKENES AND DIENES by Andrew Jonathan Bloom Anodic oxidation of dinitrogen tetroxide in acetonitrile containing lithium tetrafluoroborate gaue nitronium tetrafluoroborate in high yield and current efficiency. » Nitronium hexafluorophosphate in nitromethane and dinitrogen pentoxide in dichloromethane were similarly prepared. The electrogenerated nitration reagents were found to react with arenes, alkenes and/or silyenolethers giving the same products in similar yields to those obtained using the conventionally obtained reagents. Nitronium tetrafluoroborate in acetonitrile reacted with styrenes giving nitroacetamide products of Markounikou regiochemistry. trans-1-Phenylpropene and trans- stilbene underwent a syn addition, whilst cis-1-phenylpropene, cis-stilbene and 1-phenylcyclohexene all underwent an anti addition. The nitroacetamidation of simple alkenes gaue 1,2 and/or 1,3 adducts in low yield. Electrogenerated nitronium tetrafluoroborate in acetonitrile reacted with dienes to giue mixtures of 1,2 and 1,4 nitroacetamides. The additions onto isoprene and trans-penta-1,3-diene showed a preferential attack of the more substituted double bond. The 1,2 addition onto trans- penta-1,3-diene was syn whilst in both the 1,2 and 1,4 additions onto trans, trans hexa- 2,4-diene were non stereoselective. Oxidation of nitroacetamides with potassium permanganate or eerie aranonium nitrate under basic conditions gave acetamidoketones. Reduction of nitroacetamides with aluminium amalgam proceeded stereospecifically to give aminoacetamides. Heating the aminoacetamides caused cyclisation giving dihydroimidazoles. Mixtures of ammonium nitrate and trifluoroacetic anhydride reacted with dienes forming mixtures of nitrotrifluoroacetates. Treatment of these mixtures with a base such as potassium acetate gave 1-nitro-1,3-dienes, which were predominantly of the trans configuration. Attempted nitrotrifluoroacetoxylation of alkenes gave complex mixtures of products. The nucleophilic addition of thiophenol to trans-1-nitrobuta-1,3-diene gave mainly a 1,2 adduct, while the addition of aniline gave only a 1,4 adduct. Chapter One Introduction Nitration, the formation of a nitro-compound from an unsaturated compound, by reaction with a nitrating agent is a process of considerable popularity*. The process is commonly used to make aromatic nitro compounds, many of which are of industrial importance. Aromatic nitro compounds are used in the synthesis of explosives, 2 pharmaceuticals, dyes and fragrances, for example . (DH NO- O9N NO- HO3S SOoH NO- Trinitrotoluene Dinoserb an intermediate in an explosive a herbicide the synthesis of azo-dyes . Aliphatic nitro-compounds have considerably less industrial use. However they have become popular as 3 intermediates in research . This popularity is due to the diversity of useful reactions undergone by aliphatic nitro-compounds. R' -NH, R 'NO: NOz R-^R' NO; R' R OH Aliphatic nitro-compounds used in research are usually prepared by substitution: e.g. Nof e R^^NOo+Br or from other nitro-compounds: &g. R'Li R NO' or CdR2 R' Aromatic nitro-compounds are almost always prepared by nitration but the use of nitration of alkenes in the synthesis of aliphatic nitro-compounds is uncommon. There may be several reasons for this; many alkenes are unstable under the usual nitration conditions of concentrated 3 nitric acid or nitric acid-sulphuric acid mixtures: alkenes can undergo hydration, oxidation and polymerisation reactions in these media. Another reason is that many compounds available from nitration can be made in high yield from nitroalcohols. The nitroalcohols are prepared from condensation of a nitro-compound with an aldehyde. OCOCH OH R' R NO2 Many interesting nitration reactions, for example nitroacetamidation, are best carried out using nitronium salts which are expensive (for example N02BF^ El/g) or unpleasant to prepare and are extremely hydroscopic. The use of nitronium salts would be facilitated by an electrochemical preparation of the salts in a suitable solvent. Costs would be reduced by oxidising a cheap oxygenated-nitrogenous compound (eg. dinitrogen tetroxide, or a nitrate salt. The use of unpleasant reagents normally employed in the synthesis of nitronium salts (eg. anhydrous hydrogen fluoride, and fluorinated Lewis acids) would be avoided. The generation of the salts in the form of a solution would also allow reactions to be carried out using standard organic chemistry glassware and techniques. 4 I'l Electrochemical Nitration The standard procedure for the nitration of organic compounds involves concentrated nitric acid, either on its own or mixed with another acid.
Recommended publications
  • Chemical Hygiene Plan Manual
    CHEMICAL HYGIENE PLAN AND HAZARDOUS MATERIALS SAFETY MANUAL FOR LABORATORIES This is the Chemical Hygiene Plan specific to the following areas: Laboratory name or room number(s): ___________________________________ Building: __________________________________________________________ Supervisor: _______________________________________________________ Department: _______________________________________________________ Telephone numbers 911 for Emergency and urgent consultation 48221 Police business line 46919 Fire Dept business line 46371 Radiological and Environmental Management Revisied on: Enter a revision date here. All laboratory chemical use areas must maintain a work-area specific Chemical Hygiene Plan which conforms to the requirements of the OSHA Laboraotry Standard 29 CFR 19190.1450. Purdue University laboratories may use this document as a starting point for creating their work area specific CHP. Minimally this cover page is to be edited for work area specificity (non-West Lafayette laboratories are to place their own emergency, fire, and police telephone numbers in the space above) AND appendix K must be completed. This instruction and information box should remain. This model CHP is version 2010A; updates are to be found at www.purdue.edu/rem This page intentionally blank. PURDUE CHEMICAL HYGIENE PLAN AWARENESS CERTIFICATION For CHP of: ______________________________ Professor, building, rooms The Occupational Safety and Health Administration (OSHA) requires that laboratory employees be made aware of the Chemical Hygiene Plan at their place of employment (29 CFR 1910.1450). The Purdue University Chemical Hygiene Plan and Hazardous Materials Safety Manual serves as the written Chemical Hygiene Plan (CHP) for laboratories using chemicals at Purdue University. The CHP is a regular, continuing effort, not a standby or short term activity. Departments, divisions, sections, or other work units engaged in laboratory work whose hazards are not sufficiently covered in this written manual must customize it by adding their own sections as appropriate (e.g.
    [Show full text]
  • A Catalog of Instructional Films for College Chemistry, Serial Publication Number 42
    DOCUMENT RESUME ED 040 035 SE 007 910 AUTHOR Schrager Samuel; And Others TITLE A Catalog of Instructional Films for College Chemistry, Serial Publication Number 42. INSTITUTION Advisory Council on Coll. Chemistry. PUB DATE 69 NOTE 118p. EDRS PRICE EDRS Price MF-$0.50 HC-$6.00 DESCRIPTORS *Catalogs, *Chemistry, *College Science, *Instructional Films, Physical Sciences, *Resource Materials, Secondary School Science IDENTIFIERS Advisory Council on College Chemistry ABSTRACT This is a catalog of instructional films for college chemistry, designed for use by chemistry and other science teachers. The films in this catalog are listed in topical arrangement, which consists of (1) preparatory topics,(2) structure,(3) interaction of radiation with matter, (4) physical states,(5) formulas, equations and calculations,(6) dynamics,(7) thermochemistry, thermodynamics, and electrochemistry,(8) equilibria, (9) inorganic chemistry, (10) organic chemistry,(11) biochemistry, (12) laboratory techniques, (13) physics review,(14) miscellaneous, and(15) special interest. Each topic is divided into one or more sub-topics. Each film is listed alphabetically by title, and is identified further by its producer, length, film type (16mm, 8mm, Super 8), color or black/white, catalog number, and price. A brief description of the contents of each film is included. Starred films in the catalog are those which have been personally used and recommended by members of the panel who compiled this catalog. (LC) U S. DEPARTMENT OF HEALTH, EDUCATION & WELFARE OFFICE OF EDUCATION THIS DOCUMENT HAS BEEN REPRODUCED EXACTLY AS RECEIVED FROM THE i PERSON OR ORGANIZATION ORIGINATING IT POINTS OF VIEW OR OPINIONSI- I. STATED DO NOT NECESSARILY REPRESENT OFFICIAL OFFICE OF EDUCATION POSITION OR POLICY A CATALOG OF INSTRUCTIONAL FILMS FOR COLLEGE CHEMISTRY O v) Al CATALOG OF INSTRUCTIONAL FILMS (16mm, Super 8, and 8mm) FOR COLLEGE CHEMISTRY Advisory Council on College Chemistry Department of Chemistry Stanford University Stanford, California 94305 SERIAL PUBLICATION No.
    [Show full text]
  • CHEMICAL HYGIENE PLAN Laboratory Safety Manual Approval
    CHEMICAL HYGIENE PLAN Laboratory Safety Manual Approval Date: March 10, 2015 Prepared By: Environmental Health & Safety Table of Contents TABLE OF CONTENTS PART A: University-wide Policies and Procedures I. Introduction: ............................................................................... 2 II. Responsibilities: ......................................................................... 3 III. Information Dissemination and Employee Training. ................. 5 IV. Chemical Procurement Procedures. ........................................... 6 V. Working with Chemicals: General Safety Standard Operating Procedures. .................... 7 VI. Chemical Storage. ..................................................................... 9 VII. Disposal of Chemical Waste. ........................................................ 17 VIII. Hazard Identification: Classification & Communication. ........... 25 IX. Environmental Monitoring. ......................................................... 35 X. Personal Protective Equipment. .................................................. 37 XI. Respiratory Protection. ................................................................ 39 XII. Eye-Wash & Deluge Shower Stations. ......................................... 40 XIII. Fume Hoods. ............................................................................... 44 XIV. Fire Extinguishers. ..................................................................... 42 XV. Emergency Response. .................................................................
    [Show full text]
  • Reactions of Aromatic Compounds Just Like an Alkene, Benzene Has Clouds of  Electrons Above and Below Its Sigma Bond Framework
    Reactions of Aromatic Compounds Just like an alkene, benzene has clouds of electrons above and below its sigma bond framework. Although the electrons are in a stable aromatic system, they are still available for reaction with strong electrophiles. This generates a carbocation which is resonance stabilized (but not aromatic). This cation is called a sigma complex because the electrophile is joined to the benzene ring through a new sigma bond. The sigma complex (also called an arenium ion) is not aromatic since it contains an sp3 carbon (which disrupts the required loop of p orbitals). Ch17 Reactions of Aromatic Compounds (landscape).docx Page1 The loss of aromaticity required to form the sigma complex explains the highly endothermic nature of the first step. (That is why we require strong electrophiles for reaction). The sigma complex wishes to regain its aromaticity, and it may do so by either a reversal of the first step (i.e. regenerate the starting material) or by loss of the proton on the sp3 carbon (leading to a substitution product). When a reaction proceeds this way, it is electrophilic aromatic substitution. There are a wide variety of electrophiles that can be introduced into a benzene ring in this way, and so electrophilic aromatic substitution is a very important method for the synthesis of substituted aromatic compounds. Ch17 Reactions of Aromatic Compounds (landscape).docx Page2 Bromination of Benzene Bromination follows the same general mechanism for the electrophilic aromatic substitution (EAS). Bromine itself is not electrophilic enough to react with benzene. But the addition of a strong Lewis acid (electron pair acceptor), such as FeBr3, catalyses the reaction, and leads to the substitution product.
    [Show full text]
  • Nitration of Toluene (Electrophilic Aromatic Substitution)
    Nitration of Toluene (Electrophilic Aromatic Substitution) Electrophilic aromatic substitution represents an important class of reactions in organic synthesis. In "aromatic nitration," aromatic organic compounds are nitrated via an electrophilic aromatic substitution mechanism involving the attack of the electron-rich benzene ring on the nitronium ion. The formation of a nitronium ion (the electrophile) from nitric acid and sulfuric acid is shown below. The sulfuric acid is regenerated and hence acts as a catalyst. It also absorbs water to drive the reaction forward. Figure 1: The mechanism for the formation of a nitronium ion. The methyl group of toluene makes it around 25 times more reactive than benzene in electrophilic aromatic substitution reactions. Toluene undergoes nitration to give ortho and para nitrotoluene isomers, but if heated it can give dinitrotoluene and ultimately the explosive trinitrotoluene (TNT). Figure 2: Reaction of nitric acid and sulfuric acid with toluene. Procedure: 1. Place a 5 mL conical vial, equipped with a spin vane, in a crystallizing dish filled with ice-water placed on a stirrer. 2. Pour 1.0 mL of concentrated nitric acid into the vial. While stirring, slowly add 1.0 mL of concentrated sulfuric acid. 3. After the addition of sulfuric acid is complete, add 1.0 mL of toluene dropwise and slowly over a period of 5 minutes (slow down if you see boiling. Reaction produces a lot of heat). 4. While Stirring, allow the contents of the flask to reach the room temperature. Stir at room temperature for another 5 minutes. 5. Add 10 mL of water into a small separatory funnel.
    [Show full text]
  • Section VIII Chemical Storage
    Section VIII Chemical Storage General Considerations for Chemical Storage Carefully read the label before storing a hazardous chemical. The MSDS will also provide any special storage information and incompatibilities. Do Not Store Chemicals Alphabetically, except within a hazard class. Hazard classes that should be stored separately include: radioactive materials pyrophoric materials flammable materials oxidizing materials water reactive substances oxidizing acids inorganic acids organic acids caustics (bases) poisons (general laboratory reagents separated into organic and inorganic groups) Provide physical segregation (sills, curbs, trays) or separation between hazard classes. Keep flammable materials by themselves in approved storage cans, cabinets, or rooms. Store oxidizers well away from flammable materials. Please refer to Appendix E for an example Chemical Compatibility Chart Segregation Do not store unsegregated chemicals in alphabetical order or incompatible chemicals in close proximity to each other. The amount of space that can be placed between different chemical classes depends on the amount of storage area available in the lab suite. Do not segregate chemical classes into separate rooms unless they will only be used in that room. Segregation that disrupts normal work flow or requires more frequent transport of chemicals between labs will increase the probability of a chemical spill. Use common sense in planning chemical storage areas. Store dry reagents, liquids reagents and solutions and compressed gases in separate areas. Within each of these chemical forms segregate into hazard classes. Segregate dry reagents as follows: oxidizing solids flammable solids water reactive solids all others solids Segregate liquid reagents and solutions as follows: acid liquids caustic liquids oxidizing liquids perchloric acid solutions flammable or combustible liquids all other liquids Segregate compressed gases as follows: toxic gases flammable gases oxidizing and inert gases Once separated into hazard classes, chemicals may be stored alphabetically.
    [Show full text]
  • Study on the Formation of Dinitramide Using Mixed Acid Nitrating Agents
    Articles Indian Journal of Chemical Technology Vol. 9, May 2002, pp. 223-226 Study on the formation of dinitramide using mixed acid nitrating agents G Santhosh, S Venkatachalam*, M Kanakavel & K N Ninan Polymers and Special Chemicals Division, Vikram Sarabhai Space Centre, Trivandrum 695 022, India Received 9 August 2001; revised received 27 February 2002; accepted 21 March 2002 Nitration of ammonium sulphamate was carried out using a mixture of sulphuric acid and nitric acid at -30 to - 40°C. The mole ratio of sulphuric acid to nitric acid was varied from 0 to 4 and the extent of formation of ammonium dinitramide (ADN) was meas:red. The initial yield of ADN increases with increase of sulphuric acid content in the acid mixture and starts decreasing as the reaction time is increased. The variation of product yield with change in reaction time and total acid concentration was studied. There has been a lot of interest in recent years for the Experimental Procedure development of new high energy halogen-free Materials oxidizers like ammonium dinitramide(ADN), Ammonium sulphamate AR (SRL, Bombay) was hydrazinium nitroformate(HNF), hexanitrohexaaza­ powdered well in a mortar and pestle and was further isowurtzitane(CL-20), 1,3,3-trinitroazetidine (TNAZ) dried in vacuum. Conc. H S0 98% (Qualigens, Bombay) was used etc., having high density and heat of formation I. 2 4 as received. Ammonium dinitramide (ADN) is the ammonium salt Fuming HN0 > 98% was distilled in the laboratory of 1,1 ,3,3-tetraoxo-l ,2,3-triazapropene anion. 3 from a mixture of 1: 1 by weight of fuming HN0 Dinitramide salts are useful oxidizers for high energy 3 (92%) with conc.
    [Show full text]
  • The Effects of Nitronium Ion on Nitration, Carbonylation and Coagulation of Human Fibrinogen
    Gen. Physiol. Biophys. (2008), 27, 55–58 55 Short Communication The effects of nitronium ion on nitration, carbonylation and coagulation of human fibrinogen M. B. Ponczek, P. Nowak and B. Wachowicz Department of General Biochemistry, University of Lodz, Poland Abstract. The effect of nitronium ion on nitration, carbonylation and coagulation of human fi- brinogen (Fg) in vitro was investigated. We observed that nitration of tyrosine, induced by NO2BF4 (0.01 mmol/l), was increased. No changes in carbonylation by NO2BF4 (0.01 mmol/l) were noticed. Mentioned alterations were associated with amplified coagulation of Fg. Higher concentrations of NO2BF4 (1 and 0.1 mmol/l) triggered growth of nitration and carbonylation of Fg, but led to inhibi- tion of polymerization. Slight nitration may be responsible for increase, whereas sizable nitration and oxidation may lead to inhibition of Fg coagulation. Key words: Fibrinogen — Nitrotyrosine — Carbonyl groups — Nitronium ion — Polymerization — Coagulation Fibrinogen (Fg) is the circulating precursor of fibrin, con- (Nowak and Wachowicz 2002). There is little known about verted by thrombin to fibrin monomers, which aggregate nitration of Fg by nitronium ion (NI). The aim of our study spontaneously to form fibrin fibers (Standeven et al. 2005). was to determine the effect of NI, derived from nitronium This complex protein molecule is composed of two sets tetrafluoroborate (NO2BF4), on nitration, carbonylation and of three non-identical polypeptide chains Aα, Bβ and γ. coagulation of human Fg in vitro. All six amino-terminals meet together in a small central Fg was prepared from plasma, purchased from Lodz Blood domain E connected with two terminal domains D by long Bank, according to Doolitlle et al.
    [Show full text]
  • Continuous Flow Nitration in Miniaturized Devices
    Continuous flow nitration in miniaturized devices Amol A. Kulkarni Review Open Access Address: Beilstein J. Org. Chem. 2014, 10, 405–424. Chem. Eng. & Proc. Dev. Division, CSIR-National Chemical doi:10.3762/bjoc.10.38 Laboratory, Pune – 411 008, India, phone: +91-20-25902153 Received: 08 August 2013 Email: Accepted: 14 January 2014 Amol A. Kulkarni - [email protected] Published: 14 February 2014 This article is part of the Thematic Series "Chemistry in flow systems III". Keywords: continuous flow; flow chemistry; nitration; nitric acid; microreactors; Guest Editor: A. Kirschning tubular reactor © 2014 Kulkarni; licensee Beilstein-Institut. License and terms: see end of document. Abstract This review highlights the state of the art in the field of continuous flow nitration with miniaturized devices. Although nitration has been one of the oldest and most important unit reactions, the advent of miniaturized devices has paved the way for new opportuni- ties to reconsider the conventional approach for exothermic and selectivity sensitive nitration reactions. Four different approaches to flow nitration with microreactors are presented herein and discussed in view of their advantages, limitations and applicability of the information towards scale-up. Selected recent patents that disclose scale-up methodologies for continuous flow nitration are also briefly reviewed. Review 1 Introduction Nitration of aromatics is one of the oldest and industrially most Based on estimations of 2007 and the proposed world produc- important reactions. A reaction between an organic compound tion capacity, the overall world production of nitric acid in 2012 and a nitrating agent leads to the introduction of a nitro group is assumed to be close to 78 Mi TPA, of which 85% is used for onto a carbon, nitrogen or oxygen atom of that organic com- the production of ammonium nitrate as fertilizer and 6% for pound [1].
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 8,642,801 B2 Kong Et Al
    USOO86428O1B2 (12) United States Patent (10) Patent No.: US 8,642,801 B2 Kong et al. (45) Date of Patent: Feb. 4, 2014 (54) METHODS AND COMPOSITIONS FOR 4,528, 184 A 7, 1985 Kurono et al. TREATING AMYLOID-RELATED DISEASES 4,540,564 A 9, 1985 Bodor 4,563,470 A 1/1986 Durlach 4,593,045 A 6, 1986 Flork et al. (75) Inventors: Xianqi Kong, Dollard-des-Ormeaux 4,713,376 A 12/1987 Kuzuya et al. (CA); David Migneault, Laval (CA); 4,737,353 A 4, 1988 Flanigen et al. Isabelle Valade, Laval (CA); Xinfu Wu, 4,737,357 A 4, 1988 Lehmann et al. 4,812,512 A 3, 1989 Buendia et al. Laval (CA); Francine Gervais, Ile 4,847,082 A 7, 1989 Sabin Bizard (CA) 4.956,347 A 9, 1990 Ban et al. 5,017,566 A 5, 1991 Bodor (73) Assignee: BHI Limited Partnership, Laval, 5,023,252 A 6, 1991 HSeih Quebec (CA) 5,024,998 A 6, 1991 Bodor 5,039,794. A 8, 1991 Wier et al. Notice: Subject to any disclaimer, the term of this 5,064,923 A 11/1991 Kashihara et al. (*) 5, 112,863. A 5/1992 Hashimoto et al. patent is extended or adjusted under 35 5,124,146 A 6/1992 Neuwelt U.S.C. 154(b) by 190 days. 5,153,179 A 10, 1992 Eb1 5,164,295 A 1 1/1992 Kisilevsky et al. (21) Appl. No.: 12/613,412 5,166.320 A 11/1992 Wu et al.
    [Show full text]
  • Gas-Phase Nitronium Ion Affinities F
    Proc. Natl. Acad. Sci. USA Vol. 92, pp. 8635-8639, September 1995 Chemistry Gas-phase nitronium ion affinities F. CACACE*t, G. DE PETRIStt, F. PEPI*, AND F. ANGELELLI* *Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente Attive, Universita degli Studi di Roma "La Sapienza," Piazzale Aldo Moro, 5, 00185 Rome, Italy; and tDipartimento di Scienze Ambientali, Universita della Tuscia, v. S. C. De Lellis, 01100 Viterbo, Italy Communicated by Alfred P. Wolf, Brookhaven National Laboratory, Upton, NY, April 24, 1995 ABSTRACT Evaluation of nitronium ion-transfer equi- without further purification. The mass analyzed ion kinetic libria, L1NO' + L2 = L2NO' + L1 (where L1 and L2 are energy (MIKE) spectra were recorded using a ZAB-2F mass ligands 1 and 2, respectively) by Fourier-transform ion cyclo- spectrometer from VG Analytical (Manchester, U.K), whose tron resonance mass spectrometry and application of the chemical ionization source was fitted with a specially built device, kinetic method, based on the metastable fragmentation of designed to cool the source block, removing the heat radiated L1(NO+)L2 nitronium ion-bound dimers led to a scale of from the filament by a stream of cold N2. The spectra were relative gas-phase nitronium ion affinities. This scale, cali- recorded at temperatures ranging from 400 to 50°C, as measured brated to a recent literature value for the NO+ affinity of by a thermocouple inserted into the source block, using gaseous water, led for 18 ligands, including methanol, ammonia, mixtures of NO2 and the two ligands (L1 and L2), whose com- representative ketones, nitriles, and nitroalkanes, to absolute position was optimized to obtain the highest intensity of the NO+ affinities, that fit a reasonably linear general correlation L1(NO')L2 dimers, at total pressures in the 0.1- to 0.5-torr (1 torr when plotted vs.
    [Show full text]
  • Commerce in Explosives; 2020 Annual Those on the Annual List
    Federal Register / Vol. 85, No. 247 / Wednesday, December 23, 2020 / Notices 83999 inspection at the Office of the Secretary or synonyms in brackets. This list Black powder substitutes. and on EDIS.3 supersedes the List of Explosive *Blasting agents, nitro-carbo-nitrates, This action is taken under the Materials published in the Federal including non-cap sensitive slurry and authority of section 337 of the Tariff Act Register on January 2, 2020 (Docket No. water gel explosives. of 1930, as amended (19 U.S.C. 1337), 2019R–04, 85 FR 128). Blasting caps. and of §§ 201.10 and 210.8(c) of the The 2020 List of Explosive Materials Blasting gelatin. Commission’s Rules of Practice and is a comprehensive list, but is not all- Blasting powder. Procedure (19 CFR 201.10, 210.8(c)). inclusive. The definition of ‘‘explosive BTNEC [bis (trinitroethyl) carbonate]. materials’’ includes ‘‘[e]xplosives, BTNEN [bis (trinitroethyl) nitramine]. By order of the Commission. BTTN [1,2,4 butanetriol trinitrate]. Issued: December 18, 2020. blasting agents, water gels and detonators. Explosive materials, Bulk salutes. William Bishop, include, but are not limited to, all items Butyl tetryl. Supervisory Hearings and Information in the ‘List of Explosive Materials’ Officer. C provided for in § 555.23.’’ 27 CFR Calcium nitrate explosive mixture. [FR Doc. 2020–28458 Filed 12–22–20; 8:45 am] 555.11. Accordingly, the fact that an BILLING CODE 7020–02–P Cellulose hexanitrate explosive explosive material is not on the annual mixture. list does not mean that it is not within Chlorate explosive mixtures. coverage of the law if it otherwise meets DEPARTMENT OF JUSTICE Composition A and variations.
    [Show full text]